High performance of PtCu@TiO₂ nanocatalysts toward methanol oxidation reaction: from synthesis to molecular picture insight

The electrocatalytic production of hydrogen from methanol dehydrogenation successfully uses platinum catalysts. However, they are expensive and Pt has the tendency to be poisoned from the intermediate compounds, formed during the methanol oxidation reaction (MOR). For these two reasons, there has been active research for alternative bi- and tri-component Pt-based catalysts. Herein, PtCu nanoparticles deposited on titania were studied and proposed to be efficient MOR catalysts. The catalyst was prepared by photo-deposition of Cu on a high-surface-area TiO₂ powder support, followed by a partial galvanic displacement of the Cu deposit by platinum. The morphology and structure of the catalyst were characterized by physicochemical methods. The PtCu@TiO₂ electro-catalyst has higher intrinsic catalytic activity and comparable mass specific activity for MOR in comparison with a commercial Pt/C catalyst. The experimental analyses were complemented by density functional theory-based computations. The theoretical results revealed that the most energetically favorable Pt and Cu arrangement in the supported PtCu nanoparticles was core (Cu)-shell (Pt) and/or phase-separated. The inter-atomic interactions responsible for the bimetallic cluster stabilization on titania were highlighted from the computed electronic charge distribution.